EP2816096A1 - Method for storing excess energy - Google Patents

Method for storing excess energy Download PDF

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Publication number
EP2816096A1
EP2816096A1 EP13172441.1A EP13172441A EP2816096A1 EP 2816096 A1 EP2816096 A1 EP 2816096A1 EP 13172441 A EP13172441 A EP 13172441A EP 2816096 A1 EP2816096 A1 EP 2816096A1
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Prior art keywords
gas
clostridium
gas stream
bacteria
fermenter
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EP13172441.1A
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German (de)
French (fr)
Inventor
Thomas Dr. Haas
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Evonik Operations GmbH
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Evonik Industries AG
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Priority to EP13172441.1A priority Critical patent/EP2816096A1/en
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    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12MAPPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M43/00Combinations of bioreactors or fermenters with other apparatus
    • C12M43/04Bioreactors or fermenters combined with combustion devices or plants, e.g. for carbon dioxide removal
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12MAPPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M29/00Means for introduction, extraction or recirculation of materials, e.g. pumps
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12MAPPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M43/00Combinations of bioreactors or fermenters with other apparatus
    • C12M43/08Bioreactors or fermenters combined with devices or plants for production of electricity
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00Preparation of oxygen-containing organic compounds
    • C12P7/02Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/04Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
    • C12P7/06Ethanol, i.e. non-beverage
    • C12P7/065Ethanol, i.e. non-beverage with microorganisms other than yeasts
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00Preparation of oxygen-containing organic compounds
    • C12P7/40Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
    • C12P7/42Hydroxy-carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00Preparation of oxygen-containing organic compounds
    • C12P7/40Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
    • C12P7/54Acetic acid
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01KSTEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
    • F01K11/00Plants characterised by the engines being structurally combined with boilers or condensers
    • F01K11/02Plants characterised by the engines being structurally combined with boilers or condensers the engines being turbines
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02CGAS-TURBINE PLANTS; AIR INTAKES FOR JET-PROPULSION PLANTS; CONTROLLING FUEL SUPPLY IN AIR-BREATHING JET-PROPULSION PLANTS
    • F02C6/00Plural gas-turbine plants; Combinations of gas-turbine plants with other apparatus; Adaptations of gas- turbine plants for special use
    • F02C6/14Gas-turbine plants having means for storing energy, e.g. for meeting peak loads
    • Y02E50/17

Abstract

The invention relates to a process for the utilization of gases comprising CO and / or CO 2, comprising the process steps: A) providing a gas flow of the gas containing CO and / or CO 2, B) conversion of at least part of the gas stream into electrical energy, C) reacting at least part of the gas stream to at least one organic substance in a biotechnological, fermentative process and optionally D) Repeat the process steps B) and C).

Description

    Field of the invention
  • The invention relates to a process for the utilization of gases comprising CO and / or CO 2, comprising the process steps:
  1. A) providing a gas flow of the gas containing CO and / or CO 2 ,
  2. B) conversion of at least part of the gas stream into electrical energy,
  3. C) reacting at least part of the gas stream to at least one organic substance in a biotechnological, fermentative process and optionally
  4. D) Repeat the process steps B) and C).
State of the art
  • Power-producing power plants produce excess electricity when there is a lack of power. This must be stored accordingly in another form.
  • Thus, e.g. Pumped storage built to store excess electricity. Although pumped storage units have a large storage capacity but also a large space and space requirement and represent not inconsiderable interference in ecosystems and landscape.
  • Another approach is to store electrical energy in large batteries, especially lithium ion batteries. However, this technology requires very high investments in additional batteries whose depreciation nullifies the advantage of using the low excess electricity.
  • Other alternatives include the conversion of electricity into hydrogen, which then chemically converts CO 2 into methane. The gas then serves as energy storage. Again, significant investments in chemical transformation are needed. In addition, methane has a low energy density and is not easy to transport because it is a gas and requires either a pipeline or expensive liquefaction. Higher density can be achieved by chemical conversion to liquids. However, these processes end either in relatively low-grade substance mixtures or in methanol, which is also not well suited as an energy carrier because of its high oxygen content.
  • For fuel-based power plants, in addition to being able to convert the electricity themselves, there is also the option of diverting the energy of the fuel before generating electricity and using that energy for heat generation and subsequent heating.
  • Such a method has hitherto been used in particular where the delivery of the fuel takes place continuously and can not be throttled, as for example in power plants which draw their energy from the exhaust gas streams of industrial production facilities, such as steel mills.
  • This method has the disadvantage that heat as an energy source undergoes high losses due to lack of insulation and correspondingly requires a timely decrease. Likewise, heat is poorly transportable, so that the heat consumer must be located in the immediate vicinity of the power plant.
  • The object of the present invention is to provide a possibility for fuel-based power plants to store excess energy.
  • Description of the invention
  • Surprisingly, it has been found that the method described below is capable of solving the problem posed by the invention.
  • The present invention therefore provides a process for the utilization of gases comprising CO and / or CO 2, comprising the process steps:
    1. A) providing a gas flow of the gas containing CO and / or CO 2 ,
    2. B) conversion of at least part of the gas stream into electrical energy,
    3. C) reacting at least part of the gas stream to at least one organic substance in a biotechnological, fermentative process and optionally
    4. D) Repeat the process steps B) and C).
  • An advantage of the present invention is that the energy storage of the surplus energy occurs before the power conversion, thus a conversion step is less and thus a higher efficiency can be achieved.
  • Another advantage of the present invention is that the energy storage of the excess energy can be suspended if necessary and thus can be carried out discontinuously in time.
  • Yet another advantage of the present invention is that the energy storage of the excess energy does not require any significant start-up time, but can immediately utilize large amounts of excess energy after it has occurred.
  • Another advantage of the present invention is that the energy storage of the excess energy has low space and area requirements.
  • Yet another advantage of the present invention is that the energy store of the excess energy has a high energy density, and thus a transport of the energy is significantly facilitated.
  • A further advantage of the present invention is that the energy storage can be carried out with relatively little investment, since no sterile technology is necessary for the fermentation
  • Yet another advantage of the present invention is that the energy store of excess energy is fluid and thus easy to transport.
  • Another advantage of the present invention is that the energy storage devices are freely scalable in their dimensions.
  • Yet another advantage of the present invention is that the energy storage device can handle highly fluctuating energy flow and thus represents an ideal buffer.
  • A preferred process according to the invention is characterized in that process step B) is carried out while process step C) is carried out.
  • This means that at the same time part of the gas flow of the gas containing CO and / or CO 2 is used to generate electricity, while another part is used for the production of the organic substance.
  • The size of the respective gas streams can be continuously varied and adjusted, preferably to the extent that it requires the amount of excess energy.
  • In extreme cases, even the entire gas stream can temporarily be used to produce organic substance, which corresponds to a preferred process according to the invention, which is characterized in that process step B) is not carried out while process step C) is carried out.
  • On the other hand, even with a high power requirement, the entire gas stream can be used for conversion into electrical energy, which corresponds to a preferred method according to the invention, which is characterized in that process step C) is not carried out while process step B) is carried out.
  • The process steps B) and C) can be repeated in the process according to the invention, preferably repeated several times, which corresponds to a preferred process according to the invention, characterized in that process step D) is carried out.
  • It is advantageous according to the invention if the gas containing CO and / or CO 2 contains a reducing agent, preferably hydrogen.
  • This has the technical effect that the required redox equivalents for the biotechnological process are already included in process step C).
  • The gas containing CO and / or CO 2 is preferably selected from the group comprising synthesis gas, metallurgical gas, top gas blast furnace gas, flue gas from solid fuel or waste combustion, exhaust gas from a petroleum cracker, and gasification of cellulosic materials or coal , volatile substances.
  • Particularly suitable for the biotechnological reaction and thus preferably used according to the invention is blast furnace gas from a blast furnace in steelmaking.
  • This has the technical effect that process step C) can be operated with high yield, since this gas stream has an ideal ratio of CO, CO 2 and hydrogen.
  • In a preferred alternative embodiment of the method according to the invention, method step A) is characterized in that it comprises the use of incompletely combusted fuel from a coal or gas-fired power plant.
  • For this purpose, conventional power plants would have to be converted to the effect that they burn the fuels controlled in their degree of combustion, in power production surplus, the fuel would not be completely burned to CO 2 , but partially converted to synthesis gas, which is then used for process step C).
  • In a method which is preferred according to the invention, the power generation in method step B) comprises by means of a gas turbine and / or steam turbine process.
  • An inventively preferred method is characterized in that in step C) the organic substance is selected from organic substances comprising at least three, in particular at least four carbon atoms, preferably 3 to 26, in particular 4 to 20 carbon atoms, which in particular at 25 ° C and 1 bar Pressure are liquid.
  • This has the technical advantage that the energy density in the organic substance is high and thus more excess energy is present in easily transportable form.
  • The organic substance in process step C) is particularly preferably selected from the group 1-butanol, isobutanol, butanediol, propan-2-ol, acetone, 1-propene, butene, isobutyric acid, 2-hydroxyisobutyric acid, 2-hydroxyisobutyric acid methyl ester, straight-chain and branched Alkanoic acids which may optionally contain at least one double bond, and derivatives thereof such as butyric acid, hexanoic acid and their esters, and the corresponding alkanols.
  • The term "derivatives of alkanoic acids" is understood to mean, in particular, the reduced forms of alkanoic acid, aldehyde and alcohol, the alkanoic acid esters, the omega-hydroxylated alkanoic acids, the omega-aminated alkanoic acids, the alkanoic acid amides and the diacids and diamines.
  • An inventively preferred method is characterized in that in step C) acetogenic bacteria are used.
  • The use of acetogenic bacteria has the technical effect that the gas stream for process step C) can be temporarily reduced to a minimum, and even completely interrupted. These types of bacteria, which are used to surviving in the most adverse conditions in nature, can stay in the fermenter for a long time without any special care or food. In addition, the use of acteogenic bacteria has the technical effect that resulting surplus energy can be used immediately, as the bacteria immediately resume their metabolism when reacting the gas flow and convert the gas to organic matter.
  • The term "acetogenic bacterium" is understood to mean a bacterium which is capable of carrying out the Wood-Ljungdahl metabolic pathway and is thus able to convert CO and CO 2 and hydrogen to acetate.
  • The term "acetogenic bacterium" also encompasses those bacteria which originally do not have a Wood-Ljungdahl metabolic pathway as wild-type, but which have this only due to genetic engineering modification. Such bacteria may be, for example, E. coli cells.
  • Preferably, acetogenic bacteria used in method step C) have an increased enzyme activity of a Wood-Ljungdahl metabolic pathway enzyme due to genetic modification compared to their wild type. Preferred Wood-Ljungdahl metabolic pathway enzymes in this context are selected from CO dehydrogenases and acetyl-CoA synthetases.
  • Acetogenic bacteria, which convert CO 2 and / or CO, as well as suitable processes and process conditions, which are used in process step C) have long been known. Such processes are for example
    in the WO9800558 . WO2000014052 . WO2010115054
    in Demler et al. Reaction engineering analysis of hydrogenotrophic production of acetic acid by Acetobacterium woodii. Biotechnol Bioeng. 2011 Feb; 108 (2): 470-4 .
    in Younesia et al. Ethanol and acetate production from synthesis gas via fermentation processes using anaerobic bacterium, Clostridium Ijungdahlu. Biochemical Engineering Journal, Volume 27, Issue 2, Pages 110-119 .
    in Morinaga et al. The production of acetic acid from carbon dioxide and hydrogen by anaerobic bacterium. Journal of Biotechnology, Volume 14, Issue 2, Pages 187-194 .
    in Li Production of acetic acid from synthesis gas with mixed acetogenic microorganisms, ISSN 0493644938 .
    in Schmidt et al. A TCC 2979. Chemical Engineering Communications, 45: 1-6, 61-73 .
    in Sim et al. Optimization of acetic acid production from gas synthesis by chemolithotrophic bacterium - Clostridium aceticum using a statistical approach. Bioresour Technol. 2008 May; 99 (8): 2724-35 .
    in Vega et al. Study of gaseus substrate fermentations CO conversion to acetate 1 Batch culture or 2 continous culture. Biotechnology and Bioengineering Volume 34, Issue 6, pages 774, and 785, September 1989, respectively .
    in Cotter et al. Clostridium Ijungdahlii and Clostridium autoethanogenum using resting cells. Bioprocess and Biosystems Engineering (2009), 32 (3), 369-380 and
    in Andreesen et al. Fermentation of glucose, fructose, and xylose by Clostridium thermoaceticum. Effect of metals on growth yield, enzymes, and the synthesis of acetate from carbon dioxide. Journal of Bacteriology (1973), 114 (2), 743-51 described.
  • A person skilled in the art will be able to choose from a large number of feasible options for the design of method step C), all of which work well.
  • Particular preference is given in method step C) to acetogenic bacteria selected from the group comprising Clostridium autothenogenum DSMZ 19630, Clostridium ragsdahlei A TCC no. BAA-622, Clostridium autoethanogenum, Moorella sp HUC22-1, Moorella thermoaceticum, Moorella thermoautotrophica, Rumicoccus productus, Acetoanaerobum, Oxobacter pfennigii, Methanosarcina barkeri, Methanosarcina acetivorans, Carboxydothermus, Desulfotomaculum kutznetsovii, Pyrococcus, Peptostreptococcus, Butyribacterium methylotrophicum A TCC 33266, formicoaceticum Clostridium butyricum Clostridium, Lactobacillus delbrukii, Propionibacterium acidoprprionici, Proprionispera arboris, Anaerobierspirillum succiniproducens, Bacteroides amylophilus, Becterioides ruminicola, Thermoanaerobacter kivui , Acetobacterium woodii, Acetoanaerobium notera, Clostridium aceticum, Butyribacterium methylotrophicum, Moorella thermoacetica, Eubacterium limosum, Peptostreptococcus productus, Clostridium Ijungdahlii, Clos tridium A TCC 29797 and Clostridium carboxidivorans, especially ATCC BAA-624. A particularly suitable bacterium is Clostridium carboxidivorans, in particular such strains as "P7" and "P11". Such cells are for example in US 2007/0275447 and US 2008/0057554 described. Another particularly suitable bacterium is Clostridium Ijungdahlii, in particular strains selected from the group comprising Clostridium Ijungdahlii PETC, Clostridium Ijungdahlii ERI2, Clostridium Ijungdahlii COI and Clostridium Ijungdahlii O-52, these are described in the WO 98/00558 and WO 00/68407 and ATCC 49587, ATCC 55988 and ATCC 55989.
  • In an alternatively preferred embodiment of the process according to the invention, ethanol is formed in process step C) and, as microorganism, alkali baculum bacchi ATCC BAA-1772, Moorella sp. HUC22-1, Clostridium Ijungdahlii, Clostridium ragsdahlei, or Clostridium autoethanogenum . Corresponding instructions for carrying out process step A) are obtained, for example, from Saxena et al. Clostridium ragsdalei. By the ethanologenic acetogen.
  • Journal of Industrial Microbiology & Biotechnology Volume 38, Number 4 (2011), 513-521 . Younesi et al. Ethanol and acetate production from synthesis gas via fermentation processes using anaerobic bacterium Clostridium Ijungdahlii. Biochemical Engineering Journal Volume 27, Issue 2, 15 December 2005, Pages 110-119 . Sakai et al. Ethanol production from H2 and CO2 by a newly isolated thermophilic bacterium, Moorella sp. HUC22-1. Biotechnology Letters Volume 26, Number 20 (2004), 1607-1612 and Abrini et al. Clostridium autoethanogenum, sp. nov., anaerobic bacterium that produces ethanol from carbon monoxide. Archives of Microbiology Volume 161, Number 4 (1994), 345-351 ,
  • In an alternatively preferred embodiment of the process according to the invention, ethyl acetate is formed in process step C) and an acetogenic bacterium is used.
  • A guide for performing the method step C) of this alternative preferred embodiment is in the WO2012162321 described.
  • In an alternatively preferred embodiment of the process according to the invention, butanol is formed in process step C) and an acetogenic bacterium is used.
  • A guide for performing the method step C) of this alternative preferred embodiment is in the US20110236941 described.
  • In an alternatively preferred embodiment of the process according to the invention, hexanol is formed in process step C and an acetogenic bacterium is used.
  • A guide for performing the method step C) of this alternative preferred embodiment is in the US20100151543 described.
  • In an alternatively preferred embodiment of the process according to the invention, 2,3-butanediol is formed in process step C) and an acetogenic bacterium is used.
  • A guide for performing the method step C) of this alternative preferred embodiment is in the US20120252082 and WO2012131627 described.
  • In an alternatively preferred embodiment of the process according to the invention, isopropanol is formed in process step C) and an acetogenic bacterium is used.
  • A guide for performing the method step C) of this alternative preferred embodiment is in the US20120252083 described.
  • In an alternatively preferred embodiment of the process according to the invention, 2-hydroxyisobutyric acid is formed in process step C) and an acetogenic bacterium is used.
  • A guide for performing the method step C) of this alternative preferred embodiment is in the EP12173010 described.
  • Process step C) is carried out using acetogenic bacteria, preferably under anaerobic conditions.
  • However, it is also possible and thus represents a preferred alternative embodiment of the method according to the invention, if process step C) is carried out under aerobic conditions.
  • This is understood to mean that O 2 is present during process step C).
  • Within the scope of process step C), it is possible, for example, to supply oxygen by introducing air into the fermenter
  • In this context, it is preferred that in process step C) a detonating gas bacterium is used.
  • The use of oxyhydrogen bacteria also has the technical effect that the gas stream for process step C) can be temporarily reduced to a minimum, and even completely interrupted. These types of bacteria, which are used to surviving in the most adverse conditions in nature, can stay in the fermenter for a long time without any special care or food. In addition, the use of oxyhydrogen bacteria has the technical effect that arising surplus energy can be used immediately, because the bacteria immediately resume their metabolism when reacting the gas flow and convert the gas to organic matter.
  • The term "explosive gas bacterium" is to be understood as meaning a bacterium capable of growing chemolithoautotrophically and of building carbon skeletons with more than one C atom from H 2 and CO 2 in the presence of oxygen, the oxygen being oxidized and the oxygen being terminal Electron acceptor is used. It can according to the invention both those bacteria are used, which are inherently methanogenic bacteria, or even bacteria that have been genetically modified to methanogenic bacteria, such as an E. coli cell that has been displaced by recombinant insertion of the enzymes necessary in the position of H 2 establish and CO 2 in the presence of oxygen carbon frameworks with more than one carbon atom, wherein the hydrogen is oxidized and the oxygen is used as a terminal electron acceptor. The oxyhydrogen bacteria used in the process according to the invention are preferably those which already represent oxyhydrogen bacteria as wild-type.
  • According to the invention preferably used explosive gas bacteria are selected from the genera Achromobacter, Acidithiobacillus, Acidovorax, Alcaligenes, Anabena, Aquifex, Arthrobacter, Azospirillum, Bacillus, Bradyrhizobium, Cupriavidus, Derxia, Helicobacter, Herbaspirillum, Hydrogenobacter, Hydrogenobaculum, Hydrogenophaga "Hydrogenophilus, Hydrogenothermus, Hydrogenovibrio, Ideonella sp.O1, Kyrpidia, Metallosphaera, Methanobrevibacter, Myobacterium, Nocardia, Oligotropha, Paracoccus, Pelomonas, Polaromonas, Pseudomonas, Pseudonocardia, Rhizobium, Rhodococcus, Rhodopseudomonas, Rhodospirillum, Streptomyces, Thiocapsa, Treponema, Variovorax, Xanthobacter, Wautersia, with Cupriavidus being particularly especially from the species Cupriavidus necator (also known as Ralstonia eutropha, Wautersia eutropha, Alcaligenes eutrophus, Hydrogenomonas eutropha), Achromobacter ruhlandii, Acidithiobacillus ferrooxidans, Acidovorax facilis, Alcaligenes hydrogenophilus, Alcaligenes latus, Anabena cylind rica, Anabena oscillaroides, Anabena spp., Anabena spiroides, Aquifex aeolicus, Aquifex pyrophilus, Arthrobacter strain 11X, Bacillus schlegelii, Bradyrhizobium japonicum, Cupriavidus necator, Derxia gummosa, Escherichia coli, Heliobacter pylori, Herbaspirillum autotrophicum, Hydrogenobacter hydrogenophilus., Hydrogenobacter thermophilus, Hydrogenobaculum acidophilum, Hydrogenophaga flava, Hydrogenophaga palleronii, Hydrogenophaga pseudoflav, Hydrogenophaga taeniospiralis, Hydrogeneophilus thermoluteolus, Hydrogenothermus marinus, Hydrogenovibrio marinus, Ideonella sp. O-1, Kyrpidia Tusciae, Metallosphaera sedula, Methanobrevibactercuticularis, Mycobacterium gordonae, Nocardia autotrophica, Oligotropha carboxidivorans, Paracoccus denitrificans, Pelomonas saccharophila, Polaromonas hydrogenivorans, Pseudomonas hydrogenovora, Pseudomonas thermophila, Rhizobium japonicum, Rhodococcus opacus, Rhodopseudomonas palustris, Seliberia carboxydohydrogena, Streptomyces thermoautotrophicus , Thiocapsa roseopersicina, Treponema primitia, Variovorax paradoxus, Xanthobacter autrophicus, Xanthobacter flavus, in particular from the strains Cupriavidus necator H16, Cupriavidus necator H1 or Cupriavidus necator Z-1.
  • In an alternatively preferred embodiment of the process according to the invention, in process step C) 2-hydroxyisobutyric acid is formed and a gas-bubble bacterium is used. A guide for performing the method step C) of this alternative preferred embodiment is in the EP12173010 described.
  • In an alternatively preferred embodiment of the process according to the invention, 1-butanol is formed in process step C) and an oxyhydrogen bacterium is used.
  • A guide for performing the method step C) of this alternative preferred embodiment is in the EP13172030.2 described.
  • In an alternatively preferred embodiment of the process according to the invention, propan-2-ol is formed in process step C) and a gas-blast bacterium is used.
  • A guide for performing the method step C) of this alternative preferred embodiment is in the EP13172030.2 described.
  • In an alternatively preferred embodiment of the process according to the invention, acetone is formed in process step C) and an oxyhydrogen bacterium is used.
  • A guide for performing the method step C) of this alternative preferred embodiment is in the EP13172030.2 described.
  • In an alternatively preferred embodiment of the process according to the invention, 1-propene is formed in process step C) and a gas-bubble bacterium is used.
  • A guide for performing the method step C) of this alternative preferred embodiment is in the EP13172030.2 described.
  • In an alternatively preferred embodiment of the method according to the invention, butene is formed in process step C and a gas-blast bacterium is used.
  • A guide for performing the method step C) of this alternative preferred embodiment is in the EP13172030.2 described.
  • Another object of the present invention is an apparatus for carrying out the method according to the invention comprising:
    1. a) a gas source for continuously providing a CO and / or CO 2 -containing gas stream;
    2. b) a power conversion device for converting gas originating from the gas source into electrical energy;
    3. c) a fermenter for converting gas originating from the gas source into at least one organic substance;
    4. d) and means for selectively charging the power plant and / or the fermenter with the gas stream from the gas source.
  • The device according to the invention is preferably characterized in that the gas source is a blast furnace used in steelmaking, which continuously supplies blast furnace gas as the gas stream.
  • The power conversion device of the device according to the invention preferably comprises a generator driven by at least one turbine.
  • In this context, the turbine is preferably a gas turbine which can be operated completely or with the addition of further fuels with the gas stream.
  • According to the invention, the power conversion device preferably comprises a boiler for generating steam, which is fired with the gas stream alone or with the admixture of further fuels, and the turbine is a steam turbine operable with the steam from the boiler.
  • Preferably, the device according to the invention is characterized in that the fermenter harbors acetogenic bacteria and / or oxyhydrogen bacteria.
  • The device according to the invention is preferably characterized in that the means for selectively charging the fermenter and / or the Stromstromseinrichtug with gas flow comprising these apparatuses connecting lines and actuators.
  • In this context, it is preferred that the actuators and the lines are adapted to act on the fermenter and the power conversion device in parallel and / or in series and / or individually with the gas stream.
  • Particularly preferably, the device according to the invention is characterized in that all components of the device are incorporated into a Verbundortort.
  • Another object of the present invention is the use of the device according to the invention for carrying out the method according to the invention.
  • The use according to the invention is preferably used for the production of electrical energy and / or for the production of at least one organic substance.
  • Examples
  • The present invention will now be explained in more detail with reference to an embodiment. For this shows:
    • FIG. 1 : Device according to the invention for carrying out the method (schematically).
    • FIG. 1 shows the schematic structure of a device according to the invention for carrying out the method.
  • A gas source 1 in the form of a conventional blast furnace for steelmaking continuously delivers overhead gas at its top, which is withdrawn via a corresponding gas line 2. The blast furnace gas produced during steelmaking is a flammable dome gas, with a nitrogen content of about 45-60% and a CO content in the range of 20-30%. Furthermore, the top gas still contains about 20 - 25% CO 2 and 2 - 4% H 2 .
  • The blast furnace gas is passed to an actuator 3. This is a known per se valve, which allows to direct the gas flowing from the gas source 1 selectively via a gas line 4 in the direction of a power conversion device 5 and / or via a gas line 6 in the direction of a fermenter 7. The actuator 3 allows it In addition, the actuator 3 occupy intermediate positions, which allow a simultaneous admission of the power conversion device 5 and the fermenter 7 with the gas flow in equal parts or to different proportions.
  • The gas which has reached the power conversion device 5 is converted into electrical energy by means of a conventional gas turbine and / or steam turbine process known per se, which energy is drawn off from the power conversion device 5 as electric current 8. If a steam turbine is used, it can only be operated with the gas from the gas source 1 or with the addition of external fuels. If a steam turbine process is used, the boiler is also heated to generate steam either with the gas from the gas source 1 or additionally with the aid of external fuels. It is also possible to couple a gas turbine process to a steam turbine process within the power plant 5. The technologies described here for power generation of gas are well known in the prior art and require no further description here.
  • The components of the gas originating from the gas source 1, which are conducted via the gas line 6 in the direction of the fermenter 7, are converted therein by bacteria 9 into an organic substance 10, which is withdrawn from the fermenter 7.
  • The bacteria 9 are preferably aceotogenic bacteria or oxyhydrogen bacteria. Suitable bacteria and fermentative processes for the conversion of CO and / or CO 2 contained gases in organic substances are well known from the above cited prior art and therefore need not be described in more detail.
  • LIST OF REFERENCE NUMBERS
  • 1 Gas source / blast furnace 2 Gas pipe for blast furnace gas 3 actuator 4 Gas line in the direction of the power conversion device 5 power generation facility 6 Gas line towards the fermenter 7 fermenter 8th electrical current 9 bacteria 10 organic substance
  • Claims (25)

    1. Process for the utilization of gases containing CO and / or CO 2 comprising the process steps:
      A) providing a gas flow of the gas containing CO and / or CO 2 ,
      B) conversion of at least part of the gas stream into electrical energy,
      C) reacting at least part of the gas stream to at least one organic substance in a biotechnological, fermentative process and optionally
      D) Repeat the process steps B) and C).
    2. Method according to claim 1,
      characterized,
      that process step B) is carried out while process step C) is carried out.
    3. Method according to claim 1,
      characterized,
      that process step B) is not carried out while process step C) is carried out.
    4. Method according to claim 3,
      characterized,
      that process step D) is carried out.
    5. Method according to at least one of the preceding claims,
      characterized,
      that the gas is selected from the group consisting of synthesis gas, coke gas, blast furnace gas from blast furnaces, flue gas from the combustion of solid fuels or waste exhaust gases of a petroleum cracker, and in the gasification of cellulose-containing materials or coal released volatile substances.
    6. Method according to at least one of the preceding claims,
      characterized,
      that process step A) comprises the use of blast furnace gas from a blast furnace in steelmaking.
    7. Method according to at least one of claims 1 to 5,
      characterized,
      that method step A) comprises the use of incompletely combusted fuel of a coal or gas power plant.
    8. Method according to at least one of the preceding claims,
      characterized,
      that process step B) comprises power generation by means of a gas turbine and / or steam turbine process.
    9. Method according to at least one of the preceding claims,
      characterized,
      that in process step C) the organic substance is selected from organic substances comprising at least three, in particular at least four carbon atoms.
    10. Method according to at least one of the preceding claims,
      characterized,
      in process step C), the organic substance is selected from the group consisting of 1-butanol, isobutanol, butanediol, propane-2-ol, acetone, 1-propene, butene, isobutyric acid, 2-hydroxyisobutyric acid, 2-hydroxyisobutyric acid-Methylester, straight and branched chain alkanoic acids, which may optionally contain at least one double bond, and their derivatives such as butyric acid, hexanoic acid and their esters, and the corresponding alkanols.
    11. Method according to at least one of the preceding claims,
      characterized,
      that in process step C) acetogenic bacteria are used.
    12. Method according to claim 11,
      characterized,
      acetogenic that in method step C) bacteria selected from Clostridium autothenogenum DSMZ 19630, Clostridium ragsdahlei A TCC no. BAA-622, Clostridium autoethanogenum, Moor Ella sp HUC22-1, Moor Ella thermoaceticum, Moor Ella thermoautotrophica, Rumicoccus productus, Acetoanaerobum, Oxobacter pfennigii, Methanosarcina barkeri, Methanosarcina acetivorans, Carboxydothermus, Desulfotomaculum kutznetsovii, Pyrococcus, Peptostreptococcus, Butyribacterium methylotrophicum A TCC 33266, formicoaceticum Clostridium butyricum Clostridium, Lactobacillus delbrukii, Propionibacterium acidoprprionici, Proprionispera arboris, Anaerobierspirillum succiniproducens, Bacterioides amylophilus, Becterioides ruminicola, Thermoanaerobacter kivui, Acetobacterium woodii, Acetoanaerobium notera, Clostridium aceticum, Butyribacterium methylotrophicum, Moorella thermoacetica, Eubacterium limosum, Peptostreptococcus productus, Clostridium Ijungdahlii, Clostridium A TCC 29797 and Clostridium carboxidivorans .
    13. Method according to at least one of claims 1 to 10,
      characterized,
      that in process step C) O 2 is added and an oxyhydrogen bacterium is used.
    14. Method according to claim 13,
      characterized,
      that in process step C) an explosive gas bacterium selected from the genera Achromobacter, Acidithiobacillus, Acidovorax, Alcaligenes, Anabena, Aquifex, Arthrobacter, Azospirillum, Bacillus, Bradyrhizobium, Cupriavidus, Derxia, Helicobacter, Herbaspirillum, Hydrogenobacter, Hydrogenobaculum, Hydrogenophaga, Hydrogenophilus, Hydrogenothermus , Hydrogenovibrio, Ideonella sp. O1, Kyrpidia, Metallosphaera, Methanobrevibacter, Myobacterium, Nocardia, Oligotropha, Paracoccus, Pelomonas, Polaromonas, Pseudomonas, Pseudonocardia, Rhizobium, Rhodococcus, Rhodopseudomonas, Rhodospirillum, Streptomyces, Thiocapsa, Treponema, Variovorax, Xanthobacter, Wautersia, with Cupriavidus being particularly preferred.
    15. Apparatus for performing a method according to any one of the preceding claims, comprising:
      a) a gas source for continuously providing a CO and / or CO 2 -containing gas stream;
      b) a power conversion device for converting gas originating from the gas source into electrical energy;
      c) a fermenter for converting gas originating from the gas source into at least one organic substance;
      d) and means for selectively charging the power plant and / or the fermenter with the gas stream from the gas source.
    16. Device according to claim 15,
      characterized,
      that the gas source is a blast furnace used in steelmaking, which continuously supplies blast furnace gas as a gas stream.
    17. Device according to claim 15 or 16,
      characterized,
      that the power generation device comprises a generator driven by at least one turbine generator.
    18. Device according to claim 17,
      characterized,
      in that the turbine is a gas turbine which can be operated completely or with admixture of other fuels with the gas stream.
    19. Device according to claim 17 or 18,
      characterized,
      that the power generation means comprises a fired with the gas stream, alone or in admixture with other fuels boiler for steam generation, and that it is an operable with the steam from the boiler steam turbine with the turbine.
    20. Device according to one of claims 15 to 19,
      characterized,
      that the fermenter harbors acetogenic bacteria and / or oxyhydrogen bacteria.
    21. Device according to one of claims 15 to 20,
      characterized,
      in that the means for selectively charging the fermenter and / or the gas flow power plant comprise lines and actuators connecting these apparatuses.
    22. Device according to claim 21,
      characterized,
      that the actuators and the lines are adapted to act on the fermenter and the power generating device in parallel and / or in series and / or individually with the gas stream.
    23. Device according to one of claims 15 to 22,
      characterized,
      that all components of the device are incorporated into a Verbundortort.
    24. Use of a device according to one of Claims 15 to 23 for carrying out a method according to one of Claims 1 to 14.
    25. Use according to claim 24 for the production of electrical energy and / or for the production of at least one organic substance.
    EP13172441.1A 2013-06-18 2013-06-18 Method for storing excess energy Pending EP2816096A1 (en)

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    WO2015086154A1 (en) 2013-12-12 2015-06-18 Thyssenkrupp Ag Plant combination for producing steel and method for operating the plant combination
    US10697030B2 (en) 2013-12-12 2020-06-30 Thyssenkrupp Ag Plant combination for producing steel and method for operating the plant combination

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